CN106593373B - The method that low cost improves oil recovery factor - Google Patents
The method that low cost improves oil recovery factor Download PDFInfo
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Abstract
The present invention relates to a kind of method that low cost improves oil recovery factor, mainly solve the problems, such as that displacement composition preparation cost is high, oil displacement efficiency is low, performance resistant to high temperatures and with high salt is poor in the prior art.The method that the present invention improves oil recovery factor by using low cost, comprising the following steps: oil displacement agent and water are mixed to get oil displacement system；The oil displacement system is contacted under the conditions of 25~120 DEG C of displacement of reservoir oil temperature, total salinity > 500 mg/litre water flooding with oil bearing bed, the mother oil displacement in the oil bearing bed is come out；Wherein the oil displacement agent includes following components: 1 part of surfactant and is greater than 0 part of polymer, 0~50 part of alkali by 0~50 part；The surfactant is the technical solution of polyether carboxylic acid's salt surfactant shown in Formulas I, preferably solves the problems, such as this, can be used for high temperature and high salt sandstone oil reservoir and improves in the production of oil recovery factor.
Description
Technical field
The present invention relates to a kind of methods that low cost improves oil recovery factor.
Background technique
Chemical flooding is to change the physicochemical properties and rheological property of injection fluid by adding chemical agent in aqueous solution
And a kind of enhancements of recovery ratio are improved with the interaction characteristic of reservoir rock, it is able to fast development in China,
Main cause is that China's reservoir is that continental deposit heterogeneity is stronger, and terrestrial origin of petroleum Crude viscosity is higher, more suitable in EOR method
Together in chemical flooding.
Surfactant is exactly added in injection water by surfactant flooding technology, by reducing oil water interfacial tension
Washing oil ability is improved to improve a kind of raising recovery ratio method of oil displacement efficiency.Polymer displacement of reservoir oil tech is a kind of important raising
The method of oil recovery, compared with general water drive, polymer displacement of reservoir oil is mainly the viscosity for increasing water phase, controls oil displacement system
Mobility ratio plays the role of expanding swept volume, and for surfactant, cost is relatively low.The addition of alkali is mainly dropped
Low surfactant adsorption amount, increases the interfacial activity of surfactant.As the important technology in chemical flooding, surface is living
Property agent activity water drive, micellar solution flooding and microemulsion drive technology, polymeric surfactant is formed binary complex oil displacing technology
The ASP Oil-Displacing Technology formed with polymeric surfactant alkali has carried out some field tests at home and abroad, achieves good
Good oil displacement efficiency.Daqing oil field in 2002 has been carried out note active water increasing injection in Periphery Low Permeability Oilfield and has been tested, and 2003
Carry out note In Surfactant Solution Flood test in Periphery Low Permeability Oilfield and loudspeaker, Sa, apricot oil field Untabulated reservoirs, the purpose is to make oil-water interfaces
Tension substantially reduces, and reduces the effect on alternate surface, activation, the oil film that oil clot is detained in dispersion or removing is sticked, by flow orifice
The increase of porosity improves the flowing permeability of oil reservoir, and reaching reduces starting pressure, raising floood conformance volume and oil displacement efficiency
Effect.It was verified that active water drive can increase substantially the oil recovery factor for having put into development block, and a part is made to exist
The reserves that cannot be employed under the conditions of economic technology at present effectively put into exploitation.Since 1994, Daqing oil field using it is external into
The heavy alkylbenzene sulfonate of mouth has carried out 5 ternary composite drivings tests, improves oil recovery factor again on the basis of waterflood recovery efficiency factor
20%, and specify that ternary composite driving is the tertiary oil recovery dominant technology after polymer flooding according to this.Oil field is in ternary composite driving
After guide's field test is succeeded, it is contemplated that the problem of fouling and demulsification hardly possible takes the technology path of binary combination flooding, makes
It is host agent to the petroleum sulfonate surfactant that Shengli crude is Material synthesis, non-ionic surface active is adjuvant, can be with
Reach ultralow interfacial tension under the conditions of alkali-free, and carried out mining site pilot test in the seven area southwest Gu Dong in 2003, improves
Recovery ratio can 12%, solve the problems, such as that fouling and demulsification are difficult.
For polymer displacement of reservoir oil tech, surfactant is surfactant as the key that oil displacement agent uses
Performance and cost, especially preparation cost directly constrain its application in terms of agent for improving oilfield recovery.Mobil Oil Corporation
Patent US3927716, US4018281, US4216097 reported in succession using caustic flooding, surfactant or caustic waterflooding
Oil and using the zwitterionic surfactant displacement of reservoir oil as a result, the zwitterionic surfactant used for the carboxylic acid of different chain length
Or sulfonate type beet alkali surface activator, in total 62000~160000mg/L of mineralising, 1500~18000mg/L of calcium ions and magnesium ions
Simulation salt water in, to the interfacial tension of Texas Southern crude oil up to 10-1~10-4mN/m.The patent of Mobil Oil Corporation
US4370243 reports the oil displacement system using oil-soluble alcohol, sulphonic acid betaine and quaternary ammonium salt composition, which can both play
The effect of surfactant can also play the role of mobility control agent, and wherein quaternary ammonium salt is lipophilic group carbochain a length of 16~20
Cationic surfactant, using 2wt% octadecyl dihydroxy ethyl propyl sulfonic acid betaine salt and 1.0% n-hexyl alcohol
As oil displacement agent, after injecting 1.9PV, crude oil 100% can be displaced, but surfactant adsorption loss is larger reaches 6mg/g,
2.0% tetraethylammonium bromide of addition relative low price is as sacrifice agent to reduce surfactant adsorption on this basis
Amount.The patent US8211837 of Texas ,Usa university application, it was recently reported that be catalyzed at high temperature using the linear alcohol of cheap and simple
The long carbon alcohol that dimerization reaction is branched, and carries out sulfuric acid esterification after propylene oxide, ethylene oxide polymerization, relative to high
Expensive sulfonate surfactant, low cost has synthesized big hydrophilic group polyethers sulfate surfactant, due to big hydrophilic group
The presence of group, so that high temperature stability performance is excellent under alkaline condition for the sulfate surfactant, 0.3% branched-chain alcoho
Polyethers sulfate (C32- 7PO-6EO sulfate) with 0.3% internal olefin sulphonates (C20~24IOS) saline solution 85 DEG C with
Same amount of crude oil mixing, solubilization parameter 14.The surfactant that foreign study uses since usage amount is big, at high cost,
Receive certain limitation in practical applications as oil displacement agent.
Polyether carboxylation is an analog anion surfactants, often passes through carboxy methylation by nonionic surfactant
Modified, it has non-ionic and anionic surfactant feature concurrently, there is low surface tension, small toxicity, easily biology
The features such as degradation is a kind of multi-functional " green surfactant ".Due to its special property, Fatty Alcohol Ether Carboxylate is being changed
Cosmetic, detergent, biochemistry, pharmacy, food processing, crude oil demulsification, viscous crude drop the fields such as glutinous and have a wide range of applications.The U.S.
Patent US4818440 reports the preparation and application of fatty amide polyoxyethylene ether acetic acid, and wherein carboxymethylation reaction uses
It is that sodium hydroxide and sodium chloroacetate solid are added in batches, final polyethers conversion ratio reaches 75~80%, the crude product warp of synthesis
Peracid purification obtains the higher fatty amide polyoxyethylene ether acetic acid of purity, is applied to the daily use chemicals such as shampoo as main component and produces
In product.In this report, polyether carboxylation need to be by purification, and synthesis technology is complicated, and the three wastes of generation are more, and preparation cost is higher, and
It is not directed to the application in terms of improving oil recovery factor.
The use of Heat Resistant and Salt Tolerant Polymer is to improve another key factor of oil recovery factor.Early stage is usually used in strengthening petroleum
The industrial products of polymer flooding for exploiting (EOR) only have partially hydrolyzed polyacrylamide (PHPA) (HPAM), it dependent on high molecular weight and
The repulsive interaction of ion and highly polar side group on polymer molecular chain reaches increasing stick effect.But heavy polymer is worked as
By biggish stretching and when shear stress, it is prone to mechanical degradation and lose viscosity, injected in low-permeability rock stratum poly-
It closes particularly evident when object.Cation in aqueous solution, especially divalent ion understand the ionic group in shielded polymer, make to gather
The curling of adduct molecule chain, hydrodynamic volume, which reduces, even to be precipitated, so that increasing stick be made to substantially reduce.When stratum reservoir temperature compared with
When high (93 DEG C of >), amide groups in polyacrylamide (PAM) facile hydrolysis in high temperature aqueous solution makes the salt resistance of polymer solution
Impatient acute decline.In recent years, the research in relation to temperature-resistant and anti-salt type polyacrylamide is mainly big by introducing on main polymer chain
Side group or rigid side group improve the thermal stability of polymer, introducing inhibits the monomer of hydrolysis or the monomer insensitive to salt to be total to
Gather to improve the hydrolysis of polymer and anti-salt property, or improves the resistance to of polymer by the heat resistance and salt tolerance of hydrophobic grouping
Warm anti-salt property.
The above results show that low cost preparation displacement composition is the key that improve oil recovery factor.Using " one kettle way "
The method for preparing the salt surfactant containing polyether carboxylic acid, can greatly reduce displacement composition key component surfactant
Production cost realizes the green production of surfactant.The aqueous solution or surface-active of the surfactant of preparation simultaneously
The aqueous solution of agent and polymer, or the aqueous solution displacement composition containing surfactant and polymer and alkali is for reducing crude oil
Interfacial tension, emulsified crude oil and expansion swept volume have preferable effect, adopt so that such displacement composition improves in oil field
There is biggish application prospect in terms of yield.Therefore, for high temperature and high salt sandstone oil reservoir the characteristics of, has invented one kind in stratum temperature
Lower long-time stable structure is spent, and 10 can be formed with crude oil-2~10-4MN/m low interfacial tension, effectively improves oil recovery factor
Oil displacement agent.Exactly this displacement composition, preparation method and its application in raising oil recovery factor of the present invention.
Summary of the invention
The technical problem to be solved by the present invention is to displacement composition oil displacement efficiency is low in the prior art, preparation cost is high,
The problem of performance difference resistant to high temperatures and with high salt provides a kind of method that new low cost improves oil recovery factor.This method will contain table
The aqueous solution or surfactant of face activating agent, the aqueous solution of polymer and alkaline matter are used to drive as displacement composition
During oil, have the advantages that heat resistance is good, oil displacement efficiency is high under the high temperature conditions.
In order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of low cost improves oil recovering
The method of rate, comprising the following steps:
(1) oil displacement agent and water are mixed to get oil displacement system；
(2) by the oil displacement system under the conditions of 25~120 DEG C of displacement of reservoir oil temperature, total salinity > 500 mg/litre water flooding
It is contacted with oil bearing bed, the mother oil displacement in the oil bearing bed is come out；
Wherein, the oil displacement agent, in terms of mass fraction, including following components:
1) 1 part of surfactant；
2) 0~50 part of polymer；
3) 0~50 part of alkali；
The amount of the polymer and alkali is not 0 simultaneously；The surfactant be anion-nonionic surfactant and salt and
The mixture of alcohol；The polymer is the polymer suitable for oil extraction in oil field；The alkali be in inorganic base or organic amine at least
It is a kind of；In the oil displacement system, in terms of total oil displacement system quality, the concentration containing the surfactant be 0.001~
2.0wt%, the concentration containing the polymer are 0~1.8wt%, and the concentration containing the alkali is 0~2.0wt%.
In above-mentioned technical proposal, the surfactant be Formulas I shown in polyether carboxylic acid's salt surfactant, alcohol and salt with
Molar ratio is 1:(1~10): the mixture that (1~10) is formed；
R1X(CH2CH2O)m1(CH3CHCH2O)n(CH2CH2O)m2R2COOM, Formulas I；
X is O, R1For C8~C30Aliphatic group or by C4~C20What the saturation and unsaturated alkyl of linear chain or branched chain replaced
Phenyl ring or naphthalene nucleus；Or R1X is abietate；M1=0~50, m2=0~50, n=0~100, R2For C1~C5Alkylidene or
Hydroxyl substituted alkylene；M is selected from hydrogen, alkali metal or by formula NR4(R5)(R6)(R7) shown at least one of group；R4、R5、
R6、R7To be independently selected from H, (CH2)aOH or (CH2)b CH3One of, any integer in a=2~4, b=0~5；It is described
Salt is selected from least one of metal halide, acylate；The alcohol is selected from C1~C6Short carbon chain alcohol.
In above-mentioned technical proposal, R1Preferably C12~C24Alkyl or by C8~C12Alkyl-substituted phenyl or R1X is preferred
For abietate, R2For C1~C3Alkylidene or hydroxyl substituted alkylene.
In above-mentioned technical proposal, preferably m1=0~30, m2=0~30, n=0~30, and m1+m2 and n are not zero simultaneously,
A=2, b=0 or 1.
In above-mentioned technical proposal, the metal halide preferably is selected from alkali halide, and the acylate preferably is selected from hydroxyl
The carboxylate that base replaces.
The present invention key active ingredient of salt surfactant containing polyether carboxylic acid is polyether carboxylation I, can be by the polyethers
Carboxylate surface active agent and the salt and alcohol are obtained by mixing in required ratio, preferably with the acquisition of following preparation methods.
In above-mentioned technical proposal, the polymer is not limited strictly, can be well-known to those skilled in the art each
Kind be used for oil extraction in oil field polymer, such as but do not limit selected from xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, yin from
At least one of subtype polyacrylamide, modified polyacrylamide, hydrophobic associated polymer, polymer microballoon.
In above-mentioned technical proposal, the hydrophobic associated polymer is preferably by acrylamide, temperature-resistant anti-salt monomer or hydrophobic list
Body is copolymerized；The modified polyacrylamide is preferably copolymerized by acrylamide, temperature-resistant anti-salt monomer；Temperature-resistant anti-salt monomer
Or hydrophobic monomer can be monomer (such as styrene sulphur well-known to those skilled in the art containing big side group or rigid side group
Acid, N- alkyl maleimide, acrylamido chain alkyl sulfonic acid, chain alkyl allyl dimethyl base ammonium halide, 3- propylene
Amide groups -3 Methylbutanoic acid etc.), monomer (such as 2- acrylamide-2-methylpro panesulfonic acid), base containing hydrolysis containing resistance to salt groups
Group monomer (such as N- alkyl acrylamide), containing can inhibit amide groups hydrolysis group monomer (such as N- vinylpyrrolidone),
At least one of monomer containing hydrophobic grouping etc., temperature-resistant anti-salt monomer are preferably 2- acrylamide-2-methylpro panesulfonic acid, are dredged
Aqueous monomer is preferably 2- acrylamido dodecyl sodium sulfonate.
In above-mentioned technical proposal, acrylamide and temperature-resistant anti-salt monomer and hydrophobic monomer in the hydrophobic associated polymer
Molar ratio be 1:(0.1~40): (0.001~0.05), viscosity-average molecular weight be 500~25,000,000；More preferably acrylamide
It is 1 with the molar ratio of temperature-resistant anti-salt monomer and hydrophobic monomer: (0.1~20): (0.001~0.01), viscosity-average molecular weight 1200
~2,200 ten thousand.
In above-mentioned technical proposal, acrylamide and temperature-resistant anti-salt monomer mole preferably compares in the modified polyacrylamide
For (0.1~40): 1.
In above-mentioned technical proposal, the preferred acrylamide of the hydrophobic associated polymer, 2- acrylamido -2- methyl-prop
Sulfonic acid and 2- acrylamido dodecyl sodium sulfonate are copolymerized, acrylamide, 2- acrylamide-2-methylpro panesulfonic acid and 2-
Acrylamido dodecyl sodium sulfonate molar ratio is preferably 1:(0.1~40): (0.001~0.05), more preferably 1: (0.1~
20): (0.001~0.01).
In above-mentioned technical proposal, the modified polyacrylamide is preferably by acrylamide, 2- acrylamido -2- methyl-prop
Sulfonic acid copolymerization forms, and acrylamide and 2- acrylamide-2-methylpro panesulfonic acid molar ratio are preferably (0.1~40): 1, it is modified
The viscosity-average molecular weight of polyacrylamide is preferably 800~25,000,000.
In above-mentioned technical proposal, the inorganic base substance preferred alkali metal hydroxide, alkaline earth metal hydroxide, alkali
At least one of metal carbonate；Further preferred alkali metal hydroxide in sodium hydroxide, potassium hydroxide at least
One kind, alkaline earth metal hydroxide are selected from least one of magnesium hydroxide, calcium hydroxide, and alkali carbonate is selected from sodium carbonate
Or at least one of sodium bicarbonate.
In above-mentioned technical proposal, primary amine groups, secondary amine, tertiary amine groups, season are contained in the preferred molecule of organic basic substance
At least one of at least one of ammonium base, further preferably ethanol amine, diethanol amine, triethanolamine or triethylamine.
In above-mentioned technical proposal, the mass ratio of surfactant and polymer and alkaline matter is excellent in the displacement composition
It is selected as 1: (0~2): (0~5).
In above-mentioned technical proposal, the preparation method of the displacement composition, one of preferred embodiment the following steps are included:
(1) in the presence of basic catalyst, R1XH successively with aequum ethylene oxide, propylene oxide, reacting ethylene oxide
Obtain R1X(CH2CH2O)m1(CH3CHCH2O)n(CH2CH2O)m2H；
(2) by R1X(CH2CH2O)m1(CH3CHCH2O)n(CH2CH2O)m2H and YR2COOR3And alkali metal hydroxide or
Alkali metal alcoholates are with molar ratio 1:(1~5): (1~10) mixing, in 50~120 DEG C of reaction temperature under stirring, reaction 3~15 is small
When, obtain polyether carboxylate intermediate R1X(CH2CH2O)m1(CH3CHCH2O)n(CH2CH2O)m2R2COOR3, water is added without separating
Or alcohol water carries out saponification and obtains required surfactant mixture containing polyether carboxylation after reflux 1~10 hour；
(3) based on the mass fraction, the surfactant mixture that step (2) obtains is mixed with polymer, alkali
It is even, obtain the displacement composition.
Wherein, R3Selected from C1~C8Alkyl；Y is selected from chlorine, bromine or iodine；Basic catalyst is alkali metal hydroxide or carbon
At least one of hydrochlorate, alkaline earth metal hydroxide or carbonate；Alcohol in alcohol solution is C1~C6Short carbon chain alcohol.
The preparation method reaction equation of the salt surfactant containing polyether carboxylic acid is as follows:
In above-mentioned technical proposal, reaction temperature is preferably 120~160 DEG C in step (1), and pressure is preferably 0.30~
0.60MPa gauge pressure, basic catalyst are preferably at least one of potassium hydroxide or Anhydrous potassium carbonate.
In above-mentioned technical proposal, preferably Y is chlorine or bromine.
In above-mentioned technical proposal, R3Preferably C1~C4Alkyl.
In above-mentioned technical proposal, in step (2) alkali metal hydroxide be preferably in potassium hydroxide or sodium hydroxide extremely
Few one kind, R1X(CH2CH2O)m1(CH3CHCH2O)n(CH2CH2O)m2H and YR2COOR3And alkali metal hydroxide or alkali metal
The molar ratio of alkoxide is preferably 1:(1~3): (2~6), short carbon chain alcohol are preferably C1~C5Short carbon chain alcohol.
Salt surfactant containing polyether carboxylic acid is when M is by formula NR in order to obtain4(R5)(R6)(R7) shown in group when production
Acid can be added on the basis of step (2) and be adjusted to pH=1-2 for product, then with required NR4(R5)(R6)(R7) neutralization.
In above-mentioned technical proposal, the formula NR4(R5)(R6)(R7) shown in the corresponding alkali of group preferably be selected from ammonia, ethanol amine, two
Ethanol amine, triethanolamine, triethylamine etc..
YR2COOR3Example have but be not limited to chloracetate (such as ethyl chloroacetate), bromacetate (such as bromoacetic acid second
Ester) etc..
In above-mentioned technical proposal, the modified polyacrylamide is by acrylamide, 2- acrylamide-2-methylpro panesulfonic acid
Two kinds of monomers are formed using water solution polymerization process, can be bought from market, can also be made by the free-radical polymerized of routine.Nothing
By block copolymerization or random copolymerization, obtained product is used equally for the present invention and reaches the purpose of the present invention.The present invention is implemented
Modified polyacrylamide in example, be by acrylamide and two kinds of monomers of 2- acrylamide-2-methylpro panesulfonic acid according to mole
Than (0.1~40): being taken water as a solvent after 1 mixing and caused Raolical polymerizable with conventional radical initiators and obtained.
In above-mentioned technical proposal, the hydrophobic associated polymer is by acrylamide, 2- acrylamide-2-methylpro panesulfonic acid
It is formed, can be bought from market using water solution polymerization process with three kinds of monomers of 2- acrylamido dodecyl sodium sulfonate, it can also be with
Free-radical polymerized by routine is made.No matter block copolymerization or random copolymerization, obtained product be used equally for the present invention simultaneously
Reach the purpose of the present invention.Hydrophobic associated polymer in the embodiment of the present invention is by acrylamide, 2- acrylamido -2-
Methyl propane sulfonic acid and three kinds of monomers of 2- acrylamido dodecyl sodium sulfonate are according to molar ratio 1:(0.1~20): (0.001~
0.01) it is taken water as a solvent after mixing and is caused Raolical polymerizable with conventional radical initiators and obtained.
The key active ingredient of displacement composition of the present invention is the component 1), 2) and 3), one skilled in the art will appreciate that
For the ease of transporting and storing or scene uses etc. considers, various supply forms, such as water-free solid-state can be used
Form perhaps aqueous solid-state form perhaps aqueous cream form or aqueous solution form；Aqueous solution form includes using water
It is made into the form of concentrate, the oil displacement agent form of concentration needed for being directly made into the live displacement of reservoir oil；Wherein, there is no particular/special requirement to water,
It can be deionized water, can also be the water containing inorganic mineral, and the water containing inorganic mineral can be tap water, oil field
Layer water or oilfield injection water.
Displacement composition of the present invention can also containing foaming agent commonly used in the art, small organic molecule (such as isopropanol,
Ethylene glycol monobutyl ether, DMSO etc.) etc. oil recoveries auxiliary agent.
In above-mentioned technical proposal, the displacement composition can be using various conventional mixing methods according to aequum each component
It is mixed to get, dissolves to obtain oil displacement agent for the displacement of reservoir oil with water according to required concentration when for the displacement of reservoir oil；It can also be according to the required displacement of reservoir oil
The concentration of agent, is dissolved in water each component in the displacement composition to obtain oil displacement agent and is used for the displacement of reservoir oil.It is used in preparation
Water can be tap water, river water, seawater, oil field stratum water；Preferred water is: simulation oil field water flooding, total salinity are preferred
For 10000~250000 mg/litres.
The present invention carries out effect assessment, specific evaluation method using physical analogy displacement evaluation method are as follows:
By rock core constant temperature drying to constant weight, the gas permeability of rock core is measured；With above-mentioned simulation oil field water flooding saturated rock
The heart calculates its pore volume, and at a temperature of the displacement of reservoir oil, with crude oil saturated core, record is saturated the volume of crude oil, then with 0.1ml/
The speed of min is pumped into water flooding, is driven to aqueous up to 100%, the recovery ratio that water drive improves crude oil is calculated, then with 0.1ml/min
The obtained oil displacement agent of speed metaideophone 0.1~1PV (rock pore volume) step (3), with the speed water drive of 0.1ml/min to containing
Water 100% calculates the percentage that oil recovery factor is improved on the basis of water drive.
The preparation method for the salt surfactant containing polyether carboxylic acid that the present invention uses, due to obtaining high-purity anionic carboxylic acid
Salt surfactant is often relatively difficult, need to repeatedly be acidified purification, causes the generation of a large amount of three wastes, and use will react generation
Method of the short chain carbon alcohol as cosolvent, can not only improve the dissolubility of surfactant in water, but can save separation it is short
The interface performance of the step of chain carbon alcohol, the by-product salt of generation and possible excessive alkali Surfactant has facilitation also
Without separation, to greatly reduce the production cost of surfactant on the basis of guaranteeing surfactant properties, realize
The green production of surfactant.Polyether carboxylic acid's salt surfactant of preparation, due to containing polyethers and carboxylate radical yin simultaneously
Ionic group, to impart the excellent temperature resistance salt resistant character of the surfactant, polyether carboxylic acid's salt surfactant have compared with
Low critical micelle concentration (cmc) is lower than 1~2 order of magnitude of conventional anion surfactant, so that the surface-active
The use concentration window of agent is wider, can solve caused by gradually declining in Oil Field use process because of surfactant concentration
Interfacial tension rises problem, so that surfactant is in the migration process of underground, even if concentration is lower can still to keep ultralow oil
Water interfacial tension, so as to improve oil displacement efficiency.Modified polyacrylamide or hydrophobic association polyacrylamide in composition,
Due to the introducing of temperature-resistant anti-salt segment, the preferable temperature-resistant anti-salt performance of polymer is assigned.Alkali in composition can in crude oil
Surfactant forms soap, further increases the interfacial activity of oil displacement system, reduces surfactant in the absorption on stratum, to mentioning
High oil recovery factor has preferable effect.
The group that anionic surfactant in the present invention contains polyethers is made of EO-PO-EO segmented structure, the present invention
People has surprisingly found that, the identical and identical EO number and under conditions of PO number in other structures, the group obtained using such arrangement mode
The oil displacement efficiency for closing object is much better than EO-PO arrangement or PO-EO arrangement.
Oil displacement agent that the present invention uses and the method that low cost improves oil recovery factor, for 50~100 DEG C of formation temperature,
The simulation oil field water flooding and crude oil of 10000~250000 mg/litre of salinity, by percentage to the quality, dosage be 0.005~
0.6wt% surfactant and the above-mentioned above-mentioned alkali of hydrophobic associated polymer and 0~1.2wt% of 0~0.3wt% form the displacement of reservoir oil
Agent determines the apparent viscosity of the oil displacement agent composition solution, and the dynamical interfacial tension value between the dewatered oil of oil field can
Up to 10-2~10-4MN/m, through physical analogy displacement experiment Lab-evaluation, which can improve oil recovering on the basis of water drive
Rate achieves preferable technical effect up to 19.89%.
Detailed description of the invention
Fig. 1 is simulation core displacement experiment flow chart.Wherein, 1 is constant-flux pump, and 2 be six-way valve, and 3 be intermediate receptacle, and 4 are
Pharmacy jar, 5 be pressure pump, and 6 be six-way valve, and 7 be fill out sand tube, and 8 be graduated cylinder.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
(1) the polyether carboxylation's surfactant structure formula prepared is as follows:
242 grams of (1 mole) hexadecanols, 8.6 grams of potassium hydroxide are added into the 2L pressure reactor equipped with agitating device, add
When heat is to 80~90 DEG C, vacuum system is opened, is dehydrated 1 hour, is then replaced 3~4 times with nitrogen under a high vacuum, system is anti-
It answers temperature to be adjusted to 140 DEG C and is slowly passed through 132.0 grams of (3 moles) ethylene oxide, being slowly passed through 469.8 grams then at 150 DEG C, (8.1 rub
You) propylene oxide, pressure≤0.60MPa is controlled, 140 DEG C is adjusted the temperature to again after reaction to propylene oxide and is slowly passed through
178.2 grams of (4.05 moles) ethylene oxide control pressure≤0.40MPa.After reaction, 90 DEG C are cooled to, is removed in vacuum low
Object is boiled, is neutralized after cooling, dehydration, obtains 998.8 grams of ether of hexadecanol polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4), yield
98.5%.
(1.1 rub for 507 grams of ether of hexadecanol polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4) (0.5 mole) and 61.6 grams
You) potassium hydroxide be added equipped with mechanical stirring, thermometer and reflux condensing tube 2500 milliliters of reaction flask in, it is slow under stirring
Instill 91.9 grams of (0.55 mole) bromoacetates, control 80 DEG C of reaction temperature and react 5 hours, be added after cooling 500 grams of water and
50 gram of 95% ethyl alcohol continues to be heated to back flow reaction 4 hours.It is cooled to room temperature, required surfactant S01 is obtained, with matter
Measure percentages, hexadecanol polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4) ether acetic acid potassium 46.02%, potassium bromide
4.94%, glycolic acid potassium 0.47%, ethyl alcohol 6.04%, water 42.51%.
(2) the oil field simulated formation water of different bivalent cations and total salinity is prepared respectively, and concrete composition is shown in Table 1 institute
Show.The dewatered oil viscosity in different oil fields is shown in Table 2.
With the S01 surfactant of Shengli Oil Field simulated formation water A difference preparation steps (1) preparation, hydrophobic association polymerization
(P1 is copolymerized AM/AMPS/2- acrylamido dodecyl sodium sulfonate molar ratio=1/0.5/0.001, viscosity-average molecular weight 1930 to object
Ten thousand) it with the aqueous solution of sodium carbonate, stirs 3 hours, then three is mixed to get a kind of uniform poly- table alkali ternary system oil displacement agent,
Viscosity and oil water interfacial tension of the measurement system at 87 DEG C, and compared with S01, P1 and S01+P1 system, it is shown in Table 3.
The S01 aqueous solution for being prepared various concentration respectively with simulated formation water is measured its oil water interfacial tension to oil field dewatered oil, seen
Shown in table 4.Apparent viscosity is measured by the BROODFIELD type III viscosmeter of Brookfield company, the U.S., and interfacial tension is by beauty
The TX500 type rotating interfacial tensimeter measurement of University of Texas, state production.
(3) by artificial core constant temperature drying to constant weight, the average diameter and rock core length of rock core are measured, it is dry to weigh rock core
Weight, measures the gas permeability of rock core.With above-mentioned water flooding saturated core, its pore volume is tested.It is dehydrated with Shengli Oil Field former
Oily saturated core, the volume of record saturation crude oil.At a temperature of 87 DEG C, Produced Liquid is driven to Shengli Oil Field simulated formation water A and is contained
Water calculates the recovery ratio that water drive improves crude oil, the poly- table alkali of metaideophone 0.3PV (rock pore volume) step (2) synthesis up to 100%
After ternary system oil displacement agent, water drive to aqueous 100% calculates the percentage that oil recovery factor is improved on the basis of water drive, simultaneously
The single or binary displacement oil agent of PV identical as note compares, and is shown in Table 3.Rock core gas permeability HKGP-3 type compact rock core
The measurement of gas permeability porosity measuring instrument, the simulation core displacement experiment process of use are as shown in Figure 1.
[embodiment 2]
(1) the polyether carboxylation's surfactant structure formula prepared is as follows:
To equipped with agitating device 2L pressure reactor in be added 220 grams of (1 mole) nonyl phenols, 1.5 grams of potassium hydroxide and
4.6 grams of Anhydrous potassium carbonates carry out water removal and nitrogen displacement with [embodiment 1], system reaction temperature are adjusted to 140 DEG C and is slowly passed through
88.0 grams of (2.0 moles) ethylene oxide, are slowly passed through 585.8 grams of (10.1 moles) propylene oxide then at 150 DEG C, and control pressure≤
0.60MPa adjusts the temperature to 140 DEG C again after reaction to propylene oxide and is slowly passed through 134.2 grams of (3.05 moles) epoxy second
Alkane controls pressure≤0.40MPa.After reaction, it is post-processed with [embodiment 1], obtains Nonyl pheno (2) polyoxypropylene
(10) 991.4 grams of ether of polyoxyethylene (3), yield 97.2%.
510 grams of ether of Nonyl pheno (2) polyoxypropylene (10) polyoxyethylene (3) (0.5 mole) and 60.0 gram (1.5
Mole) equipped in 2500 milliliters of reaction flask of mechanical stirring, thermometer and reflux condensing tube, stirring is lower slow for sodium hydroxide addition
Slowly 102.4 grams of (0.75 mole) isopropyl chloracetates are instilled, 100 DEG C of reaction temperature is controlled and reacts 3 hours, be added 500 after cooling
Gram water and 70 grams of isopropanols, continue to be heated to back flow reaction 3 hours.It is cooled to room temperature, obtains required surfactant S02,
By percentage to the quality, Nonyl pheno (2) polyoxypropylene (10) polyoxyethylene (3) ether acetic acid sodium 46.21%, sodium chloride
2.43%, glycolic sodium 2.31%, isopropanol 8.03%, water 41.02%.
(2) with the S02 of Shengli Oil Field simulated formation water A difference preparation steps (1) preparation, hydrophobic associated polymer, (P1 is total to
Ten thousand) and carbonic acid poly- AM/AMPS/2- acrylamido dodecyl sodium sulfonate molar ratio=1/0.5/0.001, viscosity-average molecular weight 1930
Sodium water solution stirs 4 hours, remaining the results are shown in Table shown in 5 with [embodiment 1] (2).It is prepared respectively with oil field simulated formation water
The S02 aqueous solution of various concentration, measures its oil water interfacial tension, is shown in Table 4.
(3) laboratory simulation flooding test is carried out with [embodiment 1] (3), the results are shown in Table shown in 5.
[embodiment 3]
(1) the polyether carboxylation's surfactant structure formula prepared is as follows:
R1O(CH2CH2O)5(CHCH3CH2O)4(CH2CH2O)20CH2COONa
Wherein, R1Carbochain distribution are as follows: C1272.3%, C1427.7%.
195.0 grams of (1 mole) mixing 12/14 are added into the 2.5L pressure reactor equipped with agitating device
(C12~14) alcohol, 14.5 grams of Anhydrous potassium carbonates, water removal and nitrogen displacement are carried out with [embodiment 1], system reaction temperature is adjusted to
140 DEG C are slowly passed through 222.2 grams of (5.05 moles) ethylene oxide, and 234.9 grams of (4.05 moles) epoxies are slowly passed through then at 150 DEG C
Propane controls pressure≤0.50MPa, and after reaction to propylene oxide, cooling is slowly passed through 924 grams (21 moles) in 130 DEG C
Ethylene oxide controls pressure≤0.40MPa.After reaction, it is post-processed with [embodiment 1], 12/14 must be mixed
(C12~14) 1513.3 grams of ether of alcohol polyoxyethylene (5) polyoxypropylene (4) polyoxyethylene (20), yield 99.1%.
Mix 12/14 (C12~14) 763.5 gram (0.5 of ether of alcohol polyoxyethylene (5) polyoxypropylene (4) polyoxyethylene (20)
Mole) and 60.0 grams of (1.5 moles) sodium hydroxides 2500 milliliters equipped with mechanical stirring, thermometer and reflux condensing tube are added
In reaction flask, it is slowly dropped into 79.6 grams of (0.65 mole) ethyl chloroacetates under stirring, controls 90 DEG C of reaction temperature and reacts 4 hours,
700 grams of water and 200 gram of 95% ethyl alcohol are added after cooling, continues to be heated to back flow reaction 5 hours.It is cooled to room temperature, needed for obtaining
Surfactant S03, by percentage to the quality, mix 12/14 (C12~14) alcohol polyoxyethylene (5) polyoxypropylene (4) is poly-
Ethylene oxide (20) ether acetic acid sodium 44.53%, sodium chloride 1.65%, glycolic sodium 0.81%, 0.43% ethyl alcohol of sodium hydroxide
12.35%, water 40.23%.
(2) with the S03 of Zhongyuan Oil Field simulated formation water C preparation steps (1) preparation and hydrophobic associated polymer (P2, copolymerization
AM/AMPS/2- acrylamido dodecyl sodium sulfonate molar ratio=1/0.5/0.002, the ten thousand) aqueous solution of viscosity-average molecular weight 1800,
Stirring 4 hours, measuring temperature are 90 DEG C, remaining the results are shown in Table shown in 6 with [embodiment 1] (1).With oil field simulated formation moisture
Not Pei Zhi various concentration S03 aqueous solution, measure its interfacial tension to oil field dewatered oil, be shown in Table 4.
(3) laboratory simulation flooding test is carried out with [embodiment 1] (3), the difference is that displacement of reservoir oil temperature is 90 DEG C, as a result
It is shown in Table 6.
[embodiment 4]
(1) the polyether carboxylation's surfactant structure formula prepared is as follows:
158 grams of (1 mole) decyl alcohol, 7.2 grams of potassium hydroxide are added into the 2.5L pressure reactor equipped with agitating device, together
[embodiment 1] carries out water removal and nitrogen displacement, and system reaction temperature is adjusted to 150 DEG C and is slowly passed through 1287.6 grams (22.2 moles)
Propylene oxide controls pressure≤0.50MPa, and after reaction to propylene oxide, cooling post-processes with [embodiment 1], obtains decyl alcohol
1365.2 grams of ether of polyoxypropylene (22), yield 95.2%.
Decyl alcohol polyoxypropylene (22) ether 717 grams (0.5 moles) and 61.6 grams of (1.1 moles) potassium hydroxide are added equipped with machinery
In 2500 milliliters of reaction flask of stirring, thermometer and reflux condensing tube, 91.9 grams of (0.55 mole) bromines are slowly dropped under stirring
Ethyl acetate reacts with [embodiment 1], obtains required surfactant S04, by percentage to the quality, decyl alcohol polyoxypropylene
(22) ether acetic acid potassium 54.05%, potassium bromide 4.05%, glycolic acid potassium 0.41%, ethyl alcohol 5.07%, water 36.42%.
(2) with the S04 of Henan Oil Field simulated formation water B preparation steps (1) preparation, modified polyacrylamide, (P3, copolymerization are single
Ten thousand) and aqueous sodium carbonate molar ratio=4/1 body AM/AMPS, viscosity-average molecular weight 1500, stir 4 hours, measuring temperature 80
DEG C, remaining the results are shown in Table shown in 7 with [embodiment 1] (1).The S04 aqueous solution of various concentration is prepared with oil field simulated formation water,
Its oil water interfacial tension is measured, is shown in Table 4.
(3) laboratory simulation flooding test is carried out with [embodiment 1] (3), the difference is that displacement of reservoir oil temperature is 80 DEG C, as a result
It is shown in Table 7.
[embodiment 5]
(1) the polyether carboxylation's surfactant structure formula prepared is as follows:
328 grams of (1 mole) docosanols, 15.1 grams of anhydrous carbon are added into the 2.5L pressure reactor equipped with agitating device
Sour potassium carries out water removal and nitrogen displacement with [embodiment 1], system reaction temperature is adjusted to 140 DEG C and is slowly passed through 1122.0 grams
(25.5 moles) propylene oxide controls pressure≤0.50MPa, after reaction to propylene oxide, cooling, with after [embodiment 1]
Processing, obtains 1408.0 grams of ether of docosanol polyoxyethylene (25), yield 98.6%.
Docosanol polyoxyethylene (25) ether 714 grams (0.5 moles) and 128.8 grams of (2.3 moles) potassium hydroxide additions are matched
Have in 2500 milliliters of reaction flask of mechanical stirring, thermometer and reflux condensing tube, under stirring, is slowly dropped into 150.6 gram (1.0
Mole) Solid acid n-butyl chloroacete, it controls 110 DEG C of reaction temperature and reacts 5 hours, 400 grams of water and 50 gram of 95% ethyl alcohol is added after cooling,
Continue to be heated to back flow reaction 3 hours.It is cooled to room temperature, obtains surface activator composition S05, obtain required surfactant
S05, by percentage to the quality, docosanol polyoxyethylene (25) ether acetic acid potassium 53.17%, potassium chloride 2.63%, glycolic acid potassium
4.03%, potassium hydroxide 1.19%, mixed alcohol (ethyl alcohol+n-butanol) 8.66%, water 30.32%.
(2) with the S05 of Zhongyuan Oil Field simulated formation water D preparation steps (1) preparation and hydrophobic associated polymer (P2, copolymerization
AM/AMPS/2- acrylamido dodecyl sodium sulfonate molar ratio=1/0.5/0.002, the ten thousand) aqueous solution of viscosity-average molecular weight 1800,
Stirring 4 hours, measuring temperature are 95 DEG C, remaining the results are shown in Table shown in 8 with [embodiment 1] (1).Matched with oil field simulated formation water
The S05 aqueous solution of various concentration processed measures its interfacial tension to oil field dewatered oil, is shown in Table 4.
(3) laboratory simulation flooding test is carried out with [embodiment 1] (3), the difference is that displacement of reservoir oil temperature is 95 DEG C, as a result
It is shown in Table 8.
[embodiment 6]
(1) the polyether carboxylation's surfactant structure formula prepared is as follows:
With [embodiment 5], reaction solution is being cooled to 30 DEG C by difference, and concentrated hydrochloric acid is added and adjusts pH=2, is added 57.8
In the diethanol amine of gram (0.55 mole) and the carboxylic acid that generates, required surfactant S06 is obtained, by percentage to the quality,
Docosanol polyoxyethylene (25) ether acetic acid diethanolamine salt 53.12%, potassium chloride 6.41%, glycolic acid potassium 3.76%, mixing
Alcohol (ethyl alcohol+n-butanol) 8.15%, water 28.56%.
(2) it with [embodiment 5] (2), the results are shown in Table shown in 9, table 4.
(3) laboratory simulation flooding test is carried out with [embodiment 5] (3), the results are shown in Table shown in 9.
[embodiment 7]
Surfactant simulation saline solution is fitted into 20 milliliters of peace a word used in place name bottles, is put into baking oven after sealing, measurement is different
Ageing time rear surface activating agent simulates the oil water interfacial tension of salt water pair and crude oil, and oil water interfacial tension still may be used after finding aging
Keep 10-3~10-4The ultralow value of mN/m, is shown in Table 10.The TX500 type that interfacial tension is produced by Texas ,Usa university
Rotating interfacial tensimeter measurement.
[comparative example 1]
With [embodiment 1], the difference is that, after reaction, 30% hydrochloric acid is added in the reactive mixture and adjusts water
PH=1~3 of phase, decompression removal ethyl alcohol, isolated organic phase, that is, hexadecanol polyoxyethylene (3) polyoxypropylene (8) polyoxy second
Water is added in alkene (4) ether acetic acid, and the pH=9 of product is adjusted with 40% potassium hydroxide solution, obtains surfactant ten after purification
Six alcohol polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4) ether acetic acid S07, by percentage to the quality, hexadecanol polyoxyethylene
(3) polyoxypropylene (8) polyoxyethylene (4) ether acetic acid 45.89%, potassium hydroxide 0.87%, water 53.24%.It is surveyed with [embodiment 1]
Stand oil water interfacial tension, the results are shown in Table shown in 11.
[comparative example 2]
A certain amount of comparison surfactant is dissolved with simulation salt water A~D of different salinities, measures various concentration pair
Specific surface activator solution the results are shown in Table shown in 11 the oil water interfacial tension of several crude oil.Interfacial tension is by U.S. De Kesa
The TX500 type rotating interfacial tensimeter measurement of this university production.
In table 11, S08 is hexadecanol polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4) ether；S09 is polyoxyethylene nonyl phenyl
Ethylene (2) polyoxypropylene (10) polyoxyethylene (3) ether；S10 is 12/14 (C of mixing12~14) alcohol polyoxyethylene (5) polyoxy third
Alkene (4) polyoxyethylene (20) ether；S11: decyl alcohol polyoxypropylene (22) ether；S12: docosanol polyoxyethylene (25) ether.
[comparative example 3]
With [embodiment 1], the difference is that, it is not reacted step by step successively with propylene oxide and ethylene oxide,
But the two is mixed into the reaction of later stepping row.Slowly be passed through at 140~150 DEG C 469.8 grams of (8.1 moles) propylene oxide and
310.2 grams of (7.05 moles) ethylene oxide mixtures control pressure≤0.60MPa, remaining is identical, obtains table containing polyether carboxylation
Face active agent intermixture S13.Interface performance measurement test is carried out with [embodiment 1], the results are shown in Table shown in 11.
[comparative example 4]
With [embodiment 2], the difference is that, it is not reacted step by step successively with propylene oxide and ethylene oxide,
But the two is mixed into the reaction of later stepping row.585.8 grams of (10.1 moles) propylene oxide are slowly passed through at 140~150 DEG C
With 222.2 grams of (5.05 moles) ethylene oxide mixtures, pressure≤0.60MPa is controlled, remaining is identical, obtains containing polyether carboxylation
Surfactant mixture S14.Interface performance measurement test is carried out with [embodiment 1], the results are shown in Table shown in 11.
[comparative example 5]
With [embodiment 3], the difference is that, it is not reacted step by step successively with propylene oxide and ethylene oxide,
But the two is mixed into the reaction of later stepping row.234.9 grams of (4.05 moles) propylene oxide are slowly passed through at 120~160 DEG C
With 11144 grams of (26.0 moles) ethylene oxide mixtures, remaining is identical, obtains surfactant mixture containing polyether carboxylation
S15.Interface performance measurement test is carried out with [embodiment 1], the results are shown in Table shown in 11.
[comparative example 6]
With [embodiment 1], the difference is that, with high molecular wt. anionic polyacrylamide P4, (viscosity-average molecular weight is
Ten thousand) 2500 substitute hydrophobic associated polymer P1, remaining is identical, as a result as shown in 12.
Table 1
| Simulate salt water | Ca2+(mg/L) | Mg2+(mg/L) | TDS(mg/L) |
| A | 1200 | 400 | 32000 |
| B | 20 | 12 | 8000 |
| C | 15000 | 8000 | 180000 |
| D | 4000 | 1250 | 250000 |
Table 2
| Crude oil | Crude oil origin | Underground crude oil sticks (mPa.s) |
| I | Shengli Oil Field | 34.55. |
| II | Henan Oil Field | 3.51 |
| III | Zhongyuan Oil Field | 1.84 |
Table 3
Table 4
| Surfactant | Simulate salt water | Temperature (DEG C) | Crude oil | Concentration (%) | IFT(mN/m) |
| S01 | A | 87 | I | 0.6 | 0.00881 |
| S01 | A | 87 | I | 0.3 | 0.00052 |
| S01 | A | 87 | I | 0.1 | 0.00235 |
| S01 | A | 87 | I | 0.05 | 0.00524 |
| S01 | A | 87 | I | 0.025 | 0.00742 |
| S01 | A | 87 | I | 0.01 | 0.05271 |
| S01 | A | 87 | I | 0.005 | 0.08145 |
| S01 | A | 87 | I | 0.001 | 0.51241 |
| S01 | B | 80 | II | 0.3 | 0.01724 |
| S01 | C | 90 | III | 0.3 | 0.21483 |
| S02 | A | 87 | I | 0.3 | 0.00071 |
| S02 | A | 87 | I | 0.05 | 0.00454 |
| S02 | A | 87 | I | 0.01 | 0.01879 |
| S02 | A | 87 | I | 0.005 | 0.04117 |
| S02 | B | 80 | II | 0.3 | 0.00721 |
| S02 | C | 90 | III | 0.3 | 0.46772 |
| S03 | C | 90 | III | 0.6 | 0.00081 |
| S03 | C | 90 | III | 0.3 | 0.00095 |
| S03 | C | 90 | III | 0.05 | 0.00425 |
| S03 | C | 90 | III | 0.01 | 0.00851 |
| S03 | C | 90 | III | 0.005 | 0.02221 |
| S04 | B | 80 | II | 0.4 | 0.00078 |
| S04 | B | 80 | II | 0.2 | 0.00226 |
| S04 | B | 80 | II | 0.05 | 0.00546 |
| S04 | B | 80 | II | 0.01 | 0.01579 |
| S04 | B | 80 | II | 0.005 | 0.08635 |
| S04 | C | 90 | III | 0.1 | 0.08771 |
| S05 | D | 95 | III | 0.3 | 0.00456 |
| S05 | D | 95 | III | 0.1 | 0.00072 |
| S05 | D | 95 | III | 0.025 | 0.00231 |
| S05 | D | 95 | III | 0.01 | 0.00667 |
| S05 | D | 95 | III | 0.005 | 0.04331 |
| S05 | D | 95 | III | 0.001 | 0.52121 |
| S06 | D | 95 | III | 0.3 | 0.00322 |
| S06 | D | 95 | III | 0.1 | 0.00059 |
| S06 | D | 95 | III | 0.025 | 0.00145 |
| S06 | D | 95 | III | 0.01 | 0.00544 |
| S06 | D | 95 | III | 0.005 | 0.06331 |
| S06 | D | 95 | III | 0.001 | 0.09741 |
Table 5
Table 6
Table 7
Table 8
Table 9
Table 10
| Surfactant | Simulate salt water | Temperature (DEG C) | Crude oil | Concentration (%) | Ageing time (d) | IFT(mN/m) |
| S01 | A | 87 | I | 0.3 | 0 | 0.00052 |
| S01 | A | 87 | I | 0.3 | 30 | 0.00046 |
| S01 | A | 87 | I | 0.3 | 60 | 0.00245 |
| S01 | A | 87 | I | 0.3 | 90 | 0.00433 |
| S01 | A | 87 | I | 0.3 | 180 | 0.00288 |
| S02 | A | 87 | I | 0.3 | 0 | 0.00071 |
| S02 | A | 87 | I | 0.3 | 30 | 0.00053 |
| S02 | A | 87 | I | 0.3 | 60 | 0.00121 |
| S02 | A | 87 | I | 0.3 | 90 | 0.00457 |
| S02 | A | 87 | I | 0.3 | 180 | 0.00571 |
| S03 | C | 90 | III | 0.3 | 0 | 0.00095 |
| S03 | C | 90 | III | 0.3 | 30 | 0.00107 |
| S03 | C | 90 | III | 0.3 | 60 | 0.00367 |
| S03 | C | 90 | III | 0.3 | 90 | 0.00256 |
| S03 | C | 90 | III | 0.3 | 180 | 0.00546 |
| S04 | B | 80 | II | 0.2 | 0 | 0.00226 |
| S04 | B | 80 | II | 0.2 | 60 | 0.00322 |
| S04 | B | 80 | II | 0.2 | 90 | 0.00087 |
| S04 | B | 80 | II | 0.2 | 180 | 0.00095 |
| S05 | D | 95 | III | 0.3 | 0 | 0.00456 |
| S05 | D | 95 | III | 0.3 | 15 | 0.00302 |
| S05 | D | 95 | III | 0.3 | 60 | 0.00453 |
| S05 | D | 95 | III | 0.3 | 180 | 0.00577 |
| S06 | D | 95 | III | 0.1 | 0 | 0.00544 |
| S06 | D | 95 | III | 0.1 | 15 | 0.00489 |
| S06 | D | 95 | III | 0.1 | 60 | 0.00688 |
| S06 | D | 95 | III | 0.1 | 180 | 0.00752 |
Table 11
Table 12
Claims (8)
1. a kind of method that low cost improves oil recovery factor, comprising the following steps:
(1) oil displacement agent and water are mixed to get oil displacement system；
(2) by the oil displacement system under the conditions of 25~120 DEG C of displacement of reservoir oil temperature, total salinity > 500 mg/litre water flooding with contain
Oil formation contact, the mother oil displacement in the oil bearing bed is come out；
Wherein, the oil displacement agent, in terms of mass fraction, including following components:
1) 1 part of surfactant；
2) 0~50 part of polymer；
3) 0~50 part of alkali；
The amount of the polymer and alkali is not 0；The surfactant is the mixed of anion-nonionic surfactant and salt and alcohol
Close object；The polymer is the polymer suitable for oil extraction in oil field；The alkali is at least one of inorganic base or organic amine；Institute
It states in oil displacement system, in terms of total oil displacement system quality, the concentration containing the surfactant is 0.001~2.0wt%, contains institute
The concentration for stating polymer is 0~1.8wt%, and the concentration containing the alkali is 0~2.0wt%；
The inorganic base is selected from least one of alkali metal hydroxide, alkaline earth metal hydroxide, alkali carbonate；
The organic amine contains at least one of primary amine groups, secondary amine, tertiary amine groups, quaternary ammonium base in molecule；
The surfactant be polyether carboxylic acid's salt surfactant, alcohol and salt shown in Formulas I with molar ratio for 1:(1~10):
(1~10) mixture formed；
R1X(CH2CH2O)m1(CH3CHCH2O)n(CH2CH2O)m2R2COOM, Formulas I；
X is O, R1For C8~C30Aliphatic group or by C4~C20The phenyl ring that the saturation and unsaturated alkyl of linear chain or branched chain replace
Or naphthalene nucleus；Or R1X is abietate；M1=0~50, m2=0~50, n=0~100, R2For C1~C5Alkylidene or hydroxyl
Substituted alkylene；M is selected from hydrogen, alkali metal or by formula NR4(R5)(R6)(R7) shown at least one of group；R4、R5、R6、R7
To be independently selected from H, (CH2)aOH or (CH2)bCH3One of, any integer in a=2~4, b=0~5；The salt is selected from
At least one of metal halide, acylate；The alcohol is selected from C1~C6Short carbon chain alcohol.
2. the method that low cost according to claim 1 improves oil recovery factor, it is characterised in that the R1For C12~C24
Alkyl or by C8~C12Alkyl-substituted phenyl or R1X is abietate, R2For C1~C3Alkylidene or hydroxyl replace alkylene
Base, m1=0~30, m2=0~30, n=0~30, and m1+m2 and n are not zero, a=2, b=0 or 1 simultaneously；The metal halogen
Compound is selected from alkali halide, and acylate is selected from the carboxylate that hydroxyl replaces.
3. the method that low cost according to claim 1 improves oil recovery factor, it is characterised in that the polymer is Huang
Virgin rubber, hydroxymethyl cellulose, hydroxyethyl cellulose, anion-polyacrylamide, modified polyacrylamide, hydrophobic association polymerization
At least one of object, polymer microballoon.
4. the method that low cost according to claim 3 improves oil recovery factor, it is characterised in that the hydrophobic association is poly-
Close object to be copolymerized by acrylamide, temperature-resistant anti-salt monomer and hydrophobic monomer, the molar ratio of three kinds of monomers is 1:(0.1~20):
(0.001~0.01), viscosity-average molecular weight are 1200~22,000,000；The modified polyacrylamide is by acrylamide, 2- acryloyl
Two kinds of monomers of amido -2- methyl propane sulfonic acid are copolymerized, and two kinds of monomer mole ratios are (0.1~40): 1, viscosity-average molecular weight 800
~2,500 ten thousand.
5. the method that low cost according to claim 1 improves oil recovery factor, it is characterised in that table in the oil displacement agent
The mass ratio 1 of face activating agent and polymer and alkaline matter: (0~2): (0~5).
6. the method that a kind of any low cost of Claims 1 to 5 improves oil recovery factor, it is characterised in that the displacement of reservoir oil
The preparation method of composition, comprising the following steps:
(1) in the presence of basic catalyst, R1XH is successively obtained with aequum ethylene oxide, propylene oxide, reacting ethylene oxide
R1X(CH2CH2O)m1(CH3CHCH2O)n(CH2CH2O)m2H；
(2) by R1X(CH2CH2O)m1(CH3CHCH2O)n(CH2CH2O)m2H and YR2COOR3And alkali metal hydroxide or alkali gold
Belong to alkoxide with molar ratio 1:(1~5): (1~10) mixing is reacted 3~15 hours, is obtained in 50~120 DEG C of reaction temperature under stirring
To polyether carboxylate intermediate R1X(CH2CH2O)m1(CH3CHCH2O)n(CH2CH2O)m2R2COOR3, water or alcohol is added without separating
Water carries out saponification and obtains required surfactant mixture containing polyether carboxylation after reflux 1~10 hour；
(3) based on the mass fraction, the surfactant mixture that step (2) obtains is uniformly mixed with polymer, alkali, is obtained
To the displacement composition；
Wherein, R3Selected from C1~C8Alkyl；Y is selected from chlorine, bromine or iodine；Basic catalyst be alkali metal hydroxide or carbonate,
At least one of alkaline earth metal hydroxide or carbonate；Alcohol in alcohol solution is C1~C6Short carbon chain alcohol.
7. the method that low cost according to claim 6 improves oil recovery factor, it is characterised in that Y described in step (2)
Selected from chlorine, bromine；R3Selected from C1~C4Alkyl, alkali metal hydroxide be at least one of potassium hydroxide or sodium hydroxide,
R1X(CH2CH2O)m1(CH3CHCH2O)n(CH2CH2O)m2H and YR2COOR3And alkali metal hydroxide or alkali metal alcoholates rub
You are than being 1:(1~3): (2~6), alcohol C1~C5Short carbon chain alcohol.
8. a kind of oil displacement agent that described in any item low costs for claim 1~7 improve in the method for oil recovery factor,
It is characterized in that in terms of mass fraction, including following components:
1) 1 part of surfactant；
2) 0~50 part of polymer；
3) 0~50 part of alkali；
The amount of the polymer and alkali is not 0；The surfactant is the mixed of anion-nonionic surfactant and salt and alcohol
Close object；The polymer is the polymer suitable for oil extraction in oil field；The alkali is at least one of inorganic base or organic amine；
The inorganic base is selected from least one of alkali metal hydroxide, alkaline earth metal hydroxide, alkali carbonate；
The organic amine contains at least one of primary amine groups, secondary amine, tertiary amine groups, quaternary ammonium base in molecule；
The surfactant be polyether carboxylic acid's salt surfactant, alcohol and salt shown in Formulas I with molar ratio for 1:(1~10):
(1~10) mixture formed；
R1X(CH2CH2O)m1(CH3CHCH2O)n(CH2CH2O)m2R2COOM, Formulas I；
X is O, R1For C8~C30Aliphatic group or by C4~C20The phenyl ring that the saturation and unsaturated alkyl of linear chain or branched chain replace
Or naphthalene nucleus；Or R1X is abietate；M1=0~50, m2=0~50, n=0~100, R2For C1~C5Alkylidene or hydroxyl
Substituted alkylene；M is selected from hydrogen, alkali metal or by formula NR4(R5)(R6)(R7) shown at least one of group；R4、R5、R6、R7
To be independently selected from H, (CH2)aOH or (CH2)bCH3One of, any integer in a=2~4, b=0~5；The salt is selected from
At least one of metal halide, acylate；The alcohol is selected from C1~C6Short carbon chain alcohol；
Also, the oil displacement agent is made of the preparation method including including the following steps:
(1) in the presence of basic catalyst, R1XH is successively obtained with aequum ethylene oxide, propylene oxide, reacting ethylene oxide
R1X(CH2CH2O)m1(CH3CHCH2O)n(CH2CH2O)m2H；
(2) by R1X(CH2CH2O)m1(CH3CHCH2O)n(CH2CH2O)m2H and YR2COOR3And alkali metal hydroxide or alkali gold
Belong to alkoxide with molar ratio 1:(1~5): (1~10) mixing is reacted 3~15 hours, is obtained in 50~120 DEG C of reaction temperature under stirring
To polyether carboxylate intermediate R1X(CH2CH2O)m1(CH3CHCH2O)n(CH2CH2O)m2R2COOR3, water or alcohol is added without separating
Water carries out saponification and obtains required surfactant mixture containing polyether carboxylation after reflux 1~10 hour；
(3) based on the mass fraction, the surfactant mixture that step (2) obtains is uniformly mixed with polymer, alkali, is obtained
To the oil displacement agent；
Wherein, R3Selected from C1~C8Alkyl；Y is selected from chlorine, bromine or iodine；Basic catalyst be alkali metal hydroxide or carbonate,
At least one of alkaline earth metal hydroxide or carbonate；Alcohol in alcohol solution is C1~C6Short carbon chain alcohol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN111808595B (en) * | 2020-07-20 | 2022-09-09 | 中国石油大学(华东) | Application of biquaternary ammonium salt surfactant in viscosity reduction of thick oil |
| CN114058356B (en) * | 2020-08-06 | 2022-12-02 | 中国石油化工股份有限公司 | Thick oil viscosity reducer and thick oil viscosity reduction cold recovery method |
| CN114075433B (en) * | 2020-08-13 | 2023-04-18 | 中国石油化工股份有限公司 | Oil-soluble thick oil viscosity reducer and preparation method thereof |
| CN114540002B (en) * | 2020-11-24 | 2023-04-25 | 中国石油天然气股份有限公司 | Salt-resistant low-interfacial tension foam oil displacement agent |
| CN115466610B (en) * | 2022-11-03 | 2023-02-21 | 海域泰和(山东)能源科技有限公司 | Oil displacement agent for improving recovery ratio of sandstone oil reservoir and preparation method and application thereof |
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